CN112142885A - Low-chlorine chlorinated polypropylene with excellent solution stability at low temperature and preparation method thereof - Google Patents

Low-chlorine chlorinated polypropylene with excellent solution stability at low temperature and preparation method thereof Download PDF

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CN112142885A
CN112142885A CN202010927469.5A CN202010927469A CN112142885A CN 112142885 A CN112142885 A CN 112142885A CN 202010927469 A CN202010927469 A CN 202010927469A CN 112142885 A CN112142885 A CN 112142885A
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chlorinated polypropylene
polypropylene resin
acid
peak
propylene
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CN112142885B (en
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郑超
石滨
黎源
李同和
尚永华
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Wanhua Chemical Group Co Ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract

The invention provides low-chlorine chlorinated polypropylene with excellent solution stability at low temperature and a preparation method thereof. In the infrared spectroscopic spectrum of the raw material polypropylene adopted by the method, the wave number is 998cm‑1Peak/973 cm‑1The peak area ratio of the peak is 25-80%, and the wave number is 840cm‑1Peak/973 cm‑1The peak area ratio of the peaks is 15 to 50 percent. Refrigerating 20% toluene solution prepared from resin obtained by chlorination reaction at-20 deg.C for 30 days, and keepingThe chlorinated polypropylene resin has good fluidity and no gel or precipitation phenomenon, and the ink composition for gravure printing or offset printing, which adopts the chlorinated polypropylene resin, shows good adhesive force on a polyolefin substrate.

Description

Low-chlorine chlorinated polypropylene with excellent solution stability at low temperature and preparation method thereof
Technical Field
The invention belongs to the field of polypropylene resin, and particularly relates to low-chlorine chlorinated polypropylene with excellent solution stability at low temperature and a preparation method thereof.
Background
Thermoplastic resins include polar and nonpolar resins, and among nonpolar resins, polyolefin resins such as polypropylene and polyethylene have been widely used in recent years because they have many excellent properties such as low cost, easy molding, chemical resistance, water resistance, electrical insulation properties, and safety. The consumption of polypropylene as the second most common plastic in the world is more than 6000 million tons each year. Since polypropylene is a nonpolar plastic having low surface energy and high crystallinity, and the adhesion of ink, paint, or adhesive to the surface thereof is very poor in coating and bonding applications, chlorinated polypropylene (hereinafter referred to as CPP), which is a polypropylene substrate adhesion promoter, plays an important role.
In the preparation of chlorinated polypropylene, polypropylene is insoluble in most solvents due to its high crystallinity, and generally needs to be melted first and then dissolved. As the chlorination reaction proceeds, the chlorine content of the CPP increases, the crystallinity of the CPP decreases, the solubility in the solvent improves, but at the same time, the adhesion of the CPP to the polyolefin substrate decreases, and the higher dechlorination rate and dechlorination amount of the resin are positively correlated with the chlorine content. The low chlorine content tends to result in slow dissolution of the CPP solution, viscosity increase or gelation during storage, and loss of fluidity, so that use in colder regions or in colder conditions such as winter may be considerably limited. How to compromise solubility and adhesion becomes a key problem to be solved urgently for preparing high-quality chlorinated polypropylene.
Many of the chlorinated polypropylene resins proposed so far are produced by preparing isotactic polypropylene (hereinafter referred to as IPP) using a ziegler-natta catalyst as a polymerization catalyst, and then chlorinating the isotactic polypropylene to make IPP as a main component. On the other hand, an adhesive is disclosed in which syndiotactic polypropylene (hereinafter referred to as SPP) produced by using a metallocene compound as a polymerization catalyst is chlorinated, and chlorinated SPP is used (japanese patent No. 3045498 and japanese patent laid-open No. 7-18016). However, although the chlorinated SPP has improved solvent solubility compared to a chlorinated IPP prepared by a conventional ziegler-natta catalyst unpolymerized catalyst, it exhibits excellent adhesion only when the substrate is polypropylene, and has a disadvantage of insufficient adhesion to other materials (for example, polyvinyl chloride, polycarbonate, polyethylene terephthalate, ABS, nylon, etc.).
Patent CN200580017009 uses metallocene as polymerization catalyst to copolymerize propylene and other alpha-olefin to obtain melting point (T) measured by Differential Scanning Calorimeter (DSC)m) A chlorinated polypropylene random copolymer resin for use in the production of low-temperature baking varnishes at temperatures of 80 ℃ or below is obtained by chlorinating a propylene random copolymer at a temperature of less than 115 ℃. Patent CN201110402559 reports that isotactic polypropylene polymer prepared by metallocene catalysis, the molecular weight distribution of the polymer is less than 3, and the melting point measured by a differential scanning calorimeter is 110-140 ℃, and the CPP resin with good low-temperature fluidity can be obtained by chlorination until the chlorine content is 10-40%.
In the above-mentioned methods, a polypropylene-based raw material is synthesized by using a metallocene catalyst, the melting point of the polymer is limited, and in order to obtain a CPP having good low-temperature stability, the chlorine content is generally controlled to 25% or more, and if it is necessary to further reduce the chlorine content without impairing the solubility and low-temperature fluidity, acid modification by maleic anhydride or acrylic acid and esters thereof is required. The metallocene polypropylene with low melting point or the acid modified polypropylene has disadvantages in cost or availability, which leads to a great increase in the production cost of the low-temperature high-fluidity CPP.
Disclosure of Invention
The CPP solution requires the CPP resin to have a high chlorine content in order to obtain good low-temperature storage stability and maintain high fluidity, which in turn tends to cause the adhesion of the CPP to the polyolefin substrate and the anti-dechlorination stability and anti-yellowing property of the CPP resin itself to be impaired.
Therefore, the present invention is directed to provide a low-chlorine-content CPP resin having excellent low-temperature storage stability in solution, and a method for preparing the same.
In order to achieve the above purpose, the present invention proposes the following technical solutions:
the chlorinated polypropylene resin with low chlorine content and excellent solution stability at low temperature is obtained by chlorination reaction of raw material polypropylene, and the wave number of the raw material polypropylene in an infrared spectroscopic spectrum is 998cm-1Peak/973 cm-1The peak area ratio of the peak is 25-80%, preferably 40-75%, and the wave number is 840cm-1Peak/973 cm-1The peak area ratio of the peaks is 15% to 50%, preferably 30% to 50%, and the wave numbers refer to wave numbers within + -3 of the listed values.
According to the invention, researches show that the key technical index of synthesizing CPP by chlorinating the polypropylene raw material is the improvement of the chlorination uniformity, and the main influencing factor of the poor chlorination uniformity is that the difference of chlorination reaction rates (hereinafter referred to as chlorination accessibility difference) caused by the long-range ordered structure and the random structure of the PP raw material is large. Since 973cm-1The peak represents the in-plane oscillatory vibration of the methyl group in the polypropylene segment, and 998cm-1And 840cm-1The specific value of the peak area of the long-range ordered helical structure of the polypropylene can visually reflect the difference of the chlorination accessibility of the polypropylene raw material, and the smaller the specific value, the smaller the difference of the chlorination accessibility, and vice versa. However, when the content of the long-range ordered structure is too low, the glass transition temperature of the CPP obtained by chlorination is too low, the cohesion between the CPP molecular chains is lowered, the film-forming property at room temperature is greatly deteriorated, and the adhesion to the polyolefin substrate is also lowered. Thus, by optimizing the above peak area ratio within the preferable range, a CPP resin excellent in the combination of low-temperature dissolution stability, adhesion and film-forming property can be obtained.
In the invention, the chlorination reaction is a free radical solvent method chlorination reaction.
In the invention, the quality of chlorine element in the chlorinated polypropylene resin is controlled to be 10-25%, the solubility problem can occur when the content of chlorine element is less than 10%, the adhesive force to the base material can be reduced when the content of chlorine element is more than 25%, and the preferable content is 18-25%. Preferably, the wave number of the chlorinated polypropylene resin is 1641cm in infrared spectroscopic measurement-1Peak/977 cm-1The peak area ratio of the peaks is 0.1% to 3%, preferably in the range of 0.1% to 2%, and the wave numbers refer to the wave numbers within the range of + -3 of the listed values.
In the invention, the raw material polypropylene is one or more of homopolymerized PP, copolymer of propylene and alpha-olefin and acid modified propylene-containing polymer; preferably, the proportion of the propylene structure in the raw material polypropylene is 80% to 100%, preferably 85% to 99%, based on the total mass of the polypropylene.
In the present invention, the homopolyPP comprises PP with different stereo configuration and/or isotacticity, preferably isotactic homopolyPP with isotacticity of 50% to 95% and/or syndiotactic homopolyPP with isotacticity of 50% to 95%, more preferably isotactic homopolyPP with isotacticity of 75% to 85% and/or syndiotactic homopolyPP with isotacticity of 75% to 85%. The PP production process comprises a Ziegler-Natta and/or metallocene catalyzed polymerization process.
In the present invention, the copolymer of propylene and α -olefin is a random or block copolymer obtained by copolymerizing propylene and other α -olefin. The alpha-olefin comprises an alpha-olefin having 2 to 20 carbon atoms other than propylene, preferably one or more of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 4-methyl-1-pentene, more preferably ethylene.
In the invention, the acid-modified propylene-containing polymer is a propylene-structure-based polyolefin graft-modified with alpha, beta-unsaturated carboxylic acid and/or alpha, beta-unsaturated carboxylic acid anhydride. Preferably, the α, β -unsaturated carboxylic acid or α, β -unsaturated carboxylic anhydride comprises one or more of maleic acid, itaconic acid, citraconic acid, aconitic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, acrylic acid, methacrylic acid, fumaric acid, and mesaconic acid, preferably maleic anhydride.
In the present invention, the graft amount of the α, β -unsaturated carboxylic acid or α, β -unsaturated carboxylic acid anhydride is 0.5% to 5% based on the total mass of the acid-modified propylene-containing polymer.
In the invention, the polypropylene mainly having a propylene structure has a molecular weight range of 50,000-200,000, preferably 80,000-160,000, as characterized by Gel Permeation Chromatography (GPC). The molecular weight distribution range of GPC characterization is 1.5-3.5, and the preferred range is 1.5-2.5.
In the present invention, under the influence of ultraviolet rays and high temperature, especially in the presence of valence-variable ions and residual initiator, the CPP is easily dehydrochlorinated to form C ═ C double bonds, so that the resin is yellowed and the adhesion is reduced. In order to inhibit the deterioration influence of variable valence metal ions and residual initiators on the thermal stability of the CPP, one or both of a metal ion shielding agent and an antioxidant with the effect of complexing metal ions are added into a reaction solution before post-treatment, so that the thermal stability of the CPP can be effectively improved. The chlorinated polypropylene resin contains a metal ion shielding agent and/or an antioxidant with a metal ion complexing effect; preferably, the metal ion shielding agent comprises one or more of 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl ] hydrazine, triethanolamine, pentamethyl diethylenetriamine and 2, 2-bipyridine, and the metal ions are introduced into metal/alloy equipment and comprise iron ions, copper ions, chromium ions, nickel ions and the like; preferably, the antioxidant having a complexing metal ion effect comprises one or more of the antioxidants IrganoxMD 1024, NouguardXL-1, RIANOX MD-1024, RIANOX MD-697 and RIANOX 1019; preferably, the addition amount of the metal ion shielding agent and the antioxidant with the function of complexing metal ions is 0.1 to 0.5 percent of the weight of the chlorinated polypropylene resin.
The invention also provides a method for preparing the chlorinated polypropylene resin.
In the method for preparing the chlorinated polypropylene resin, the raw material polypropylene is dissolved in a chlorine-containing solvent, chlorine is introduced, and the chlorinated polypropylene is synthesized through a free radical substitution reaction. For example, the chlorine-containing solvent may be chloroform, chlorobenzene, or the like, e.g., the radical substitution reaction may be initiated by one or more of light, heat, and a radical initiator.
In one embodiment, the method of preparing the chlorinated polypropylene resin may be:
(1) adding chlorobenzene and polypropylene into a reaction kettle, heating, preserving heat to completely dissolve the polypropylene, then cooling, and introducing nitrogen for blowing;
(2) adding azodiisobutyronitrile AIBN, continuing to purge with nitrogen, closing the nitrogen, introducing chlorine gas for reaction, naturally cooling, and introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system;
(3) pumping the reaction liquid into a flash tank, concentrating the reaction liquid, adding an antioxidant and tert-butylphenyl glycidyl ether, pumping into a double-screw extruder provided with a reduced pressure distillation exhaust port to remove the solvent chlorobenzene, extruding the chlorinated polypropylene resin into a linear shape, and cooling with water. Then, the pellets were pelletized by a water-cooled pelletizer to obtain solid pellets of a chlorinated polypropylene resin.
Hydrogen chloride generated by desolvation chlorine further promotes dechlorination, so that an epoxy compound is required to be added as a stabilizer before the CPP reaction liquid is subjected to high-temperature desolvation, and the adding amount is preferably 1-7% of the weight of the CPP resin. The epoxy stabilizer preferably has good compatibility with the CPP resin, and the epoxy stabilizer includes but is not limited to: epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing natural vegetable oil having an unsaturated group with a peracid such as peracetic acid; epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid; an epoxidized alicyclic compound represented by epoxidized tetrahydrophthalic acid ester; bisphenol a glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like, which are obtained by condensing bisphenol a or a polyhydric alcohol with epichlorohydrin; and monoepoxy compounds represented by butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, and the like.
The reaction solution to which the stabilizer is added is supplied to an extruder with an exhaust port equipped with a suction device for desolventizing at the screw shaft portion, is solidified, and is dissolved in the solvent. The method for forming the solid state may employ a known method, and for example, an extruder with an exhaust port provided with an underwater shear granulator in the outlet portion of the extruder, a granulator for cutting up strand-like resin, and the like may be used.
In one embodiment, the method of evaluating low temperature stability may be: dissolving the chlorinated polypropylene resin solid particles into a toluene solvent to prepare a solution, freezing and storing for 30 days, observing the dissolution state of the solution and testing the viscosity, wherein the specific process comprises the following steps:
preparing a solution: adding a chlorinated polypropylene resin sample into a solvent toluene or ethyl acetate, stirring at room temperature by a high-speed stirring dispersion machine until the chlorinated polypropylene resin sample is completely dissolved, and then sealing and storing by using a reagent bottle to be tested.
And (3) low-temperature storage: the prepared chlorinated polypropylene solution is subpackaged in glass bottles, then the glass bottles are placed in a refrigerator to be frozen for 30 days at the low temperature of minus 20 ℃, the liquidity of the solution is observed once every 5 days, and the result is the statistics of the results of 3 parallel tests.
The solvent used for testing the low-temperature stability is preferably an aromatic solvent such as toluene or xylene, and as other non-aromatic solvents, ester solvents such as ethyl acetate or butyl acetate, ketone solvents such as methyl ethyl ketone or methyl isobutyl ketone, aliphatic solvents such as n-hexane or heptane, and alicyclic solvents such as cyclohexane, methylcyclohexane or ethylcyclohexane may be used similarly to the aromatic solvents.
Another object of the present invention is to provide use of the chlorinated polypropylene resin.
In the present invention, the chlorinated polypropylene resin is used for an ink composition for gravure printing or offset printing, which exhibits good adhesion on a polyolefin substrate.
The pressures are absolute pressures.
The technical scheme provided by the invention has the following beneficial effects:
(1) the CPP resin with excellent low-temperature dissolution stability is obtained by optimizing the peak area ratio of the long-range ordered helical structure of the polypropylene, and can keep good fluidity and no gel after being frozen at the low temperature of-20 ℃ for more than 30 days.
(2) By optimizing the peak area ratio of the characteristic peak of the conjugated C ═ C double bond, the obtained product has excellent color and adhesion performance, the color number of a 20 wt% toluene solution is less than 150Hazen, and the adhesion of a coating film by a cross-cut film method is more than or equal to 96%.
Drawings
FIG. 1 is an IR spectrum of a polypropylene raw material used in example 1 of the present invention, wherein the inset is a partial enlargement of a characteristic peak;
FIG. 2 is an IR spectrum of a chlorinated polypropylene synthesized in example 1 of the present invention, wherein the inset is a partial enlargement of the characteristic peaks;
FIG. 3 is an IR spectrum of a chlorinated polypropylene synthesized in example 2 of the present invention, wherein the inset is a partial enlargement of the characteristic peaks;
FIG. 4 is an IR spectrum of a chlorinated polypropylene synthesized in example 3 of the present invention, wherein the inset is a local magnification of the characteristic peaks.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials used in the examples of the present invention and the comparative examples are as follows:
metallocene random copolymerization polypropylene, adopting Exxon Mobil, Liandedsel and Dow products;
low isotactic polypropylene, adopting Japanese brightening L-MODUTMA series of products;
metallocene homopolymerized polypropylene, adopting a Liande Basel brand HM2015 product;
chlorine gas from chlor-alkali plants in Wanhua chemical industry park, with water content < 50 ppm;
a free radical initiator, namely azobisisobutyronitrile AIBN, wherein a reagent with the purity of 99 percent of the alatin is adopted;
a free radical initiator, namely dibenzoyl peroxide (BPO), adopts a reagent with the purity of 99 percent of the alatin;
1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propylacyl ] hydrazine, adopting TCI to analyze pure reagent;
antioxidant RIANOX MD-1024, which is produced by the Lianlong New Material Co., Ltd;
tert-butylphenyl glycidyl ether, using a reagent having an Inokay purity of 99%.
The preparation method of the maleic anhydride grafted polypropylene raw material comprises the following steps:
(1) equipment manufacturers: coperion, model: CTE20 PLUS, nine section barrel, screw diameter 20mm, length to diameter ratio 26.
(2) The operation parameters are as follows: 2000g of polypropylene versify 4200, 60g of maleic anhydride, 40g of cumene hydroperoxide and 10g N, N-Dimethylformamide (DMF) in the particle size range of 10 to 100 mesh were first mixed thoroughly and fed to a CTE20 PLUS twin-screw extruder with a residence time of 10 minutes. The reaction was carried out at a cylinder temperature of 190 ℃ (barrel 1 to barrel 8), and unreacted maleic anhydride and DMF were removed by degassing in barrel 8 to obtain a maleic anhydride-modified propylene random copolymer. The reaction starting material used in example 5.
(3) And (3) measuring the grafting rate of the maleic anhydride, namely, cutting a certain amount of the graft into particles, heating, refluxing and dissolving the particles in a certain amount of dimethylbenzene, then precipitating the particles by using acetone, extracting the precipitate (the polypropylene melt graft containing part of unreacted maleic anhydride) by using acetone in a Soxhlet extractor for 12 hours to remove unreacted maleic anhydride monomers, extracting the extract (the polypropylene melt graft containing part of unreacted maleic anhydride), and performing vacuum drying in a vacuum drying oven to obtain a purified sample.
Purified graft product sample preparation the halide tablet process was used. Dissolving the grafted product in toluene, placing 1 drop in 40mg KBr powder, grinding, oven drying at about 70 deg.C for 1 hr, preparing two parallel sample tablets with tablet press, measuring with infrared spectrometer, measuring air space as background, and scanning for 32 times (1442 cm)-1is-CH2Absorption peak of (1), 1750cm-1And 1855cm-1The absorption peak of the acid anhydride is shown. And calculating the grafting rate of the maleic anhydride according to the ratio of the peak areas of the two. The calculation formula is as follows:
G％＝3.33×A1/A2
wherein: g% is maleic anhydride graft ratio, A11740 and 1890cm-1Area of peak of (A)2Is 1417 and 1513cm-1Peak area of (a). The maleic anhydride grafting of the grafting modified polypropylene is obtained by calculationThe branching rate was 2.5%.
The infrared analysis apparatus and method are as follows:
(1) fourier transform Infrared Spectroscopy, Nicolet corporation, USA, model iS10 FTIR, spectral range 4000cm-1～400cm-1Resolution of 1cm-132 scans, beam splitter KBr, detector DTGS.
(2) The American Nicolet company OMINIC software and TQ Analyst 8.0 quantitative analysis software.
(3) Tablet press, LabTech USA.
The chlorination reaction rate and chlorine content were determined as follows: taking 0.5-1 mL of deionized water absorption liquid (hydrochloric acid) of reaction tail gas, adopting a Mettler RM50 refractometer, and measuring refraction under the condition of 20 ℃, wherein the concentration C of hydrochloric acid is (n)20-1.333)/0.0023 x 100%, so that the chlorine content of the HCl product in the reaction process and the reaction utilization rate of the chlorine can be further calculated, and the chlorine content W is mH2O*C/(1-C)*35.5/36.5/(mPP+mHCl*35.5/36.5-mHCl36.5). 100, chlorine utilization by the final HCl produced and Cl consumed by the reaction2Calculating the total amount of the compound, wherein the formula A is mHCl*71/36.5/mCl2。
Example 1
This example synthesizes chlorinated polypropylene as follows:
(1) the product of Widamei 6502, which is commercially available from Exxon Mobil polypropylene, 6502 uses ethylene as a comonomer, and the propylene structure accounts for 87 percent. The wave number peak value is 998cm through infrared characterization-1/973cm-1The peak area ratio of (A) was 37%, and the wave number peak was 840cm-1/973cm-1The peak area ratio of (A) was 26%. The infrared spectrum is shown in figure 1.
Adding 10kg of chlorobenzene and 1.5kg of Vidamia 6502 (melting index is 45g/10min, weight average molecular weight is 15 ten thousand, molecular weight distribution is 2.2) into a 20L enamel reaction kettle, heating to 120 ℃, preserving heat for 20min to completely dissolve polypropylene, then cooling to 70 ℃, and introducing nitrogen to blow for 20 min;
(2) adding 2.5g of Azobisisobutyronitrile (AIBN), continuing to purge for 10min by nitrogen, closing the nitrogen, introducing chlorine at the rate of 7.5g/min at the reaction temperature of 75 ℃, reacting for 95min until the chlorine content in the chlorinated polypropylene reaches 18%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) the reaction solution was pumped into a flash tank, concentrated to 30 wt% at 1mBar absolute pressure, then added with 4.0g of antioxidant RIANOX MD-1024 (equivalent to 0.2 wt% of the mass of chlorinated polypropylene) and 19.8g (equivalent to 1 wt% of the mass of chlorinated polypropylene) of tert-butylphenyl glycidyl ether, and then pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin was strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-1 #. The infrared spectrum is shown in FIG. 2, and the peak value of wave number is 1641cm after infrared spectroscopic analysis-1/977cm-1The peak area ratio of (A) was 0.2%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 18 percent by weight. CPP-1# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured, as follows, and the results are shown in Table 1.
Preparing a solution: a chlorinated polypropylene resin sample (200 g) is taken, added with solvent toluene (800 g) or solvent ethyl acetate (800 g), stirred at room temperature by a high-speed stirring dispersion machine (1000rpm) until being completely dissolved, and then sealed and stored by a reagent bottle to be tested.
And (3) low-temperature storage: the prepared chlorinated polypropylene solution is subpackaged into 3 batches of 200mL solution, the solution is filled in a 250mL glass bottle, then the solution is placed in a refrigerator and is frozen at the low temperature of minus 20 ℃ for 30 days, the fluidity of the solution is observed once every 5 days, and the result is the statistics of the results of 3 times of parallel tests.
Solution viscosity: the temperature of a measuring cylinder is controlled by a Bohler flying DV2T rotational viscometer through a low-temperature circulating bath, about 20mL of test sample is added, a rotor is selected to control the torque between 40% and 60%, and the viscosity readings are read. The results are shown in Table 1.
Color number of product solution: chlorinated polypropylene particles were dissolved in toluene to prepare a 20 wt% solution, and the Hazen color number of the sample solution was measured with a quartz sample cell using a BYK model LCS IV colorimeter. The results are shown in Table 2.
Coating adhesion force: the chlorinated polypropylene was dissolved in toluene to prepare a 20 wt% solution, 100g of the solution was kneaded with 2g of titanium dioxide and 0.5g of aurora red C pigment by a sand mill for 2 hours, and then a rigid polypropylene translucent plate (homopolypropylene T30S 300mm 150mm 3mm) was used as a coating substrate, and a 50 μm-thick film was coated by a 50 μm-wet film maker, dried to the surface at room temperature, and then placed in an 80 ℃ forced air oven for drying for 2 hours, and then taken out and naturally cooled to obtain a coating film test piece having a resin layer thickness of about 10 μm. Cutting the resin layer coating surface of the coating test piece into 10 × 10 small grids with 1mm intervals by using a grid knife, adhering the small grids by using a 3M adhesive tape special for an adhesion test, peeling the adhesive tape along the direction of 180 degrees, reading the number of the remaining grids, namely the adhesion value of the grid method, and taking the average value of three tests as a final result. The results are shown in Table 2.
Example 2
This example synthesizes chlorinated polypropylene as follows:
(1) adopts Japanese gloss grade low-grade regular polypropylene and a commercial grade product L-MODUTMS600, is homopolymerized polypropylene, and has the isotacticity of about 76%. The wave number peak value is 998cm through infrared characterization-1/973cm-1The peak area ratio of (A) is 55%, and the wave number peak value is 840cm-1/973cm-1The peak area ratio of (A) was 40%.
10kg of chlorobenzene and 1.5kg of L-MODU were added to a 20L enamel reactorTMS600 (the melting index is 350g/10min, the weight average molecular weight is 7.5 ten thousand, the molecular weight distribution is 2.5), heating to 120 ℃, preserving the heat for 20min to completely dissolve the polypropylene, then cooling to 80 ℃, and introducing nitrogen to blow for 20 min;
(2) adding 2.5 dibenzoyl peroxide (BPO), continuing nitrogen purging for 10min, closing the nitrogen, introducing chlorine at the rate of 7.5g/min at the reaction temperature of 75 ℃, reacting for 140min until the chlorine content in the chlorinated polypropylene reaches 25%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) pumping the reaction solution into a flash tank, concentrating the reaction solution to 30 wt% under the absolute pressure of 1mBar, and adding 4.0g of metal ion shielding agent 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl acyl]Hydrazine (corresponding to 0.2% by weight of the chlorinated polypropylene) and 19.8g (corresponding to 1% by weight of the chlorinated polypropylene) of tert-butylphenyl glycidyl ether are pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin is strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-2 #. The infrared spectrum is shown in FIG. 3, and the peak value of wave number is 1641cm after infrared spectroscopic analysis-1/977cm-1The peak area ratio of (A) was 0.5%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 25 percent by weight. CPP-2# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured as in example 1, and the results are shown in Table 1. The color number and adhesion test were carried out as in example 1, and the results are shown in Table 2.
Example 3
This example synthesizes chlorinated polypropylene as follows:
(1) adopts Japanese gloss grade low-grade regular polypropylene and a commercial grade product L-MODUTMS901, is homopolypropylene, with an isotacticity of about 83%. The wave number peak value is 998cm through infrared characterization-1/973cm-1The peak area ratio of (A) was 69%, and the wave number peak was 840cm-1/973cm-1The peak area ratio of (A) was 47%.
10kg of chlorobenzene and 1.5kg of L-MODU were added to a 20L enamel reactorTMS901 (melt index is 50g/10min, weight average molecular weight is 13 ten thousand, molecular weight distribution is 2.4), heating to 120 ℃, preserving heat for 20min to completely dissolve polypropylene, then cooling to 95 ℃, and introducing nitrogen to blow for 20 min;
(2) adding 2.5g of dibenzoyl peroxide (BPO), continuing nitrogen purging for 10min, closing the nitrogen, introducing chlorine at a rate of 7.5g/min at a reaction temperature of 75 ℃, reacting for 140min until the chlorine content in the chlorinated polypropylene reaches 25%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) pumping the reaction solution into a flash tank, concentrating the reaction solution to 30 wt% under the absolute pressure of 1mBar, and adding 4.0g of metal ion shielding agent 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl acyl]Hydrazine (corresponding to 0.1% by weight of the mass of chlorinated polypropylene) and 19.8g (corresponding to 1% by weight of the mass of chlorinated polypropylene) of tert-butylphenyl glycidyl ether are pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin is strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-3 #. The infrared spectrum is shown in FIG. 4, and the peak value of wave number is 1641cm after infrared spectroscopic analysis-1/977cm-1The peak area ratio of (A) was 2.5%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 25 percent by weight. CPP-3# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured as in example 1, and the results are shown in Table 1. The color number and adhesion test were carried out as in example 1, and the results are shown in Table 2.
Example 4
This example synthesizes chlorinated polypropylene as follows:
(1) adopts the Dow random copolymerization polypropylene and the commercial product versifyTM4200 and 4200 use ethylene as comonomer, and the propylene structure accounts for 91%. The wave number peak value is 998cm through infrared characterization-1/973cm-1The peak area ratio of (A) is 75%, and the wave number peak value is 840cm-1/973cm-1The peak area ratio of (A) was 51%.
10kg of chlorobenzene and 1.5kg of versify were charged into a 20L enamel reactorTM4200 (melting index of 25g/10min), heating to 120 deg.C, maintaining for 20min to completely dissolve polypropylene, cooling to 80 deg.C, and purging with nitrogen for 20 min;
(2) adding 2.5 dibenzoyl peroxide (BPO), continuing nitrogen purging for 10min, closing the nitrogen, introducing chlorine at the rate of 7.5g/min at the reaction temperature of 75 ℃, reacting for 140min until the chlorine content in the chlorinated polypropylene reaches 25%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) pumping the reaction solution into a flash tank, concentrating the reaction solution to 30 wt% under the absolute pressure of 1mBar, and adding 4.0g of metal ion shielding agent 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl acyl]Hydrazine (corresponding to 0.2% by weight of the chlorinated polypropylene) and 19.8g (corresponding to 1% by weight of the chlorinated polypropylene) of tert-butylphenyl glycidyl ether are pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin is strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-4 #. Through infrared spectroscopic analysis, the wave number peak value is 1641cm-1/977cm-1The peak area ratio of (A) was 0.4%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 25 percent by weight. CPP-4# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured as in example 1, and the results are shown in Table 1. The color number and adhesion test were carried out as in example 1, and the results are shown in Table 2.
Example 5
This example synthesizes chlorinated polypropylene as follows:
(1) maleic anhydride-modified versify having a grafting rate of 2.5% prepared as described aboveTM4200 product, infrared characterization, wave number peak 998cm-1/973cm-1The peak area ratio of (A) was 71%, and the wave number peak was 840cm-1/973cm-1The peak area ratio of (A) was 45%.
10kg of chlorobenzene and 1.5kg of maleic anhydride grafted versify were added to a 20L enamel reactorTM4200 (melting index of 25g/10min), heating to 120 deg.C, maintaining for 20min to completely dissolve polypropylene, cooling to 80 deg.C, and purging with nitrogen for 20 min;
(2) adding 2.5 dibenzoyl peroxide (BPO), continuing nitrogen purging for 10min, closing the nitrogen, introducing chlorine at the rate of 7.5g/min at the reaction temperature of 75 ℃, reacting for 67min until the chlorine content in the chlorinated polypropylene reaches 12%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) pumping the reaction solution into a flash tank, concentrating the reaction solution to 30 wt% under the absolute pressure of 1mBar, and then adding 10g of 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl acyl as a metal ion shielding agent]Hydrazine (corresponding to 0.5% by weight of the mass of chlorinated polypropylene) and 19.8g (corresponding to 1% by weight of the mass of chlorinated polypropylene) of tert-butylphenyl glycidyl ether are pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin is strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-5 #. Through infrared spectroscopic analysis, the wave number peak value is 1641cm-1/977cm-1The peak area ratio of (A) was 0.1%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 12 percent by weight. CPP-5# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured as in example 1, and the results are shown in Table 1. The color number and adhesion test were carried out as in example 1, and the results are shown in Table 2.
Comparative example 1
In contrast to example 3, this comparative example differs from example 3 in that: the raw material of the Vidamia 6502 is replaced by Liande Barssel homopolymerized PP HM2105 (melt index is 100g/10min, weight average molecular weight is 17 ten thousand, molecular weight distribution is 1.8), and the wave number peak value is 998cm through infrared characterization-1/973cm-1The peak area ratio of (A) was 97%, and the wave number peak was 840cm-1/973cm-1The peak area ratio of (A) was 57%. The other experimental conditions were the same.
This comparative example synthesizes chlorinated polypropylene as follows:
(1) adding 10kg of chlorobenzene and 1.5kg of polypropylene (PP) HM2015 into a 20L enamel reaction kettle, heating to 120 ℃, keeping the temperature for 20min to completely dissolve the polypropylene, then cooling to 95 ℃, and introducing nitrogen to blow for 20 min;
(2) adding 2.5g of dibenzoyl peroxide (BPO), continuing nitrogen purging for 10min, closing the nitrogen, introducing chlorine at a rate of 7.5g/min at a reaction temperature of 75 ℃, reacting for 140min until the chlorine content in the chlorinated polypropylene reaches 25%, naturally cooling, introducing nitrogen to purge residual chlorine and hydrogen chloride in the reaction system, and purging for 90 min;
(3) pumping the reaction solution into a flash tank, concentrating the reaction solution to 30 wt% under the absolute pressure of 1mBar, and adding 4.0g of metal ion shielding agent 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propyl acyl]Hydrazine (corresponding to 0.2% by weight of the chlorinated polypropylene) and 19.8g (corresponding to 1% by weight of the chlorinated polypropylene) of tert-butylphenyl glycidyl ether are pumped into a twin-screw extruder equipped with a vacuum distillation vent to remove the solvent chlorobenzene, and the chlorinated polypropylene resin is strand-extruded and cooled with water. Then, granulating by using a water-cooled granulator to obtain chlorinated polypropylene resin solid particles CPP-6 #. Through infrared spectroscopic analysis, the wave number peak value is 1641cm-1/977cm-1The peak area ratio of (A) was 2%.
The reaction utilization rate of the chlorine is 97 percent, and the chlorine content in the reaction end product is 25 percent by weight. CPP-6# was dissolved in toluene solvent to prepare a 20 wt% solution, which was stored at-20 ℃ for 30 days, and the dissolved state was observed and the viscosity was measured as in example 1, and the results are shown in Table 1. The color number and adhesion test were carried out as in example 1, and the results are shown in Table 2.
The results of the summary of the solubility properties of each CPP sample are listed in table 1.
TABLE 1 Low-temperature storage stability and viscosity of CPP solutions prepared in examples and comparative examples
Figure BDA0002668928690000181
CPP6# swelled only in ethyl acetate and failed to dissolve
As can be seen from Table 1, in comparative example 1, the proportion of the chain segment having a regular helical structure contained in polypropylene was high, and the obtained CPP6# was not soluble in the dissolution of esters such as ethyl acetate, and gel was found after storage at-20 ℃ for 5 days, and the solution completely lost fluidity.
The color number and adhesion results for each CPP resin are listed in table 2.
TABLE 2 color number and coating film adhesion of CPP solutions prepared in examples and comparative examples
Sample numbering Color number (Hazen) Adhesion (Baige method,%)
CPP 1# 55 96
CPP 2# 67 98
CPP 3# 118 99
CPP 4# 59 99
CPP 5# 41 100
CPP 6# 121 95
As shown above, the proportion of the stereoregular spiral structure chain segment in the propylene polymer is controlled in a lower range, the obtained product has excellent chlorination uniformity, and the CPP resin can achieve excellent solubility and low-temperature solvent storage stability at a lower chlorine content; in addition, the addition of an auxiliary agent capable of passivating ions reduces dechlorination of the CPP in a high-temperature post-treatment process, so that the content of rigid C-C double bond structures is reduced, and the improvement of the solubility of the CPP and the low-temperature stability of the solution are also facilitated.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. A chlorinated polypropylene resin with low chlorine content and excellent solution stability at low temperature is obtained by chlorination reaction of raw material polypropylene, and is characterized in that the wave number in an infrared spectroscopic spectrum of the raw material polypropylene is 998cm-1Peak/973 cm-1The peak area ratio of the peak is 25-80%, preferably 40-75%, and the wave number is 840cm-1Peak/973 cm-1The peak area ratio of the peaks is 15-50%, preferably 30-50%, and the wave number refers to the wave number within the range of +/-3 of the listed values.
2. The chlorinated polypropylene resin according to claim 1, wherein the chlorination reaction is a free radical solvent method chlorination reaction;
and/or the mass of chlorine element in the chlorinated polypropylene resin is controlled to be 10-25%, preferably 18-25%;
preferably, the wave number of the chlorinated polypropylene resin is 1641cm in infrared spectroscopic measurement-1Peak/977 cm-1The peak area ratio of the peaks is 0.1% to 3%, preferably in the range of 0.1% to 2%, and the wave numbers refer to the wave numbers within the range of + -3 of the listed values.
3. The chlorinated polypropylene resin according to claim 1 or 2, wherein the raw polypropylene is one or more of homopolypropylene, a copolymer of propylene and α -olefin, and an acid-modified propylene-containing polymer;
preferably, the proportion of the propylene structure in the raw material polypropylene is 80% to 100%, preferably 85% to 99%, based on the total mass of the polypropylene.
4. Chlorinated polypropylene resin according to any one of claims 1-3, wherein the homopolyPP comprises PP of different stereo configuration and/or isotacticity, preferably isotactic homopolyPP with isotacticity in the range of 50-95% and/or syndiotactic homopolyPP with isotacticity in the range of 50-95%, more preferably isotactic homopolyPP with isotacticity in the range of 75-85% and/or syndiotactic homopolyPP with isotacticity in the range of 75-85%.
5. The chlorinated polypropylene resin according to any one of claims 1 to 4, wherein the copolymer of propylene with an α -olefin is a random or block copolymer obtained by copolymerizing propylene with other α -olefin;
and/or the alpha-olefin comprises an alpha-olefin having 2 to 20 carbon atoms other than propylene, preferably one or more of ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene and 4-methyl-1-pentene, more preferably ethylene.
6. The chlorinated polypropylene resin according to any one of claims 1 to 5, wherein the acid-modified propylene-containing polymer is a propylene structure-based polyolefin graft-modified with an α, β -unsaturated carboxylic acid and/or an α, β -unsaturated carboxylic acid anhydride;
preferably, the α, β -unsaturated carboxylic acid or α, β -unsaturated carboxylic anhydride comprises one or more of maleic acid, itaconic acid, citraconic acid, aconitic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, acrylic acid, methacrylic acid, fumaric acid, and mesaconic acid, preferably maleic anhydride;
and/or the grafting amount of the alpha, beta-unsaturated carboxylic acid or the alpha, beta-unsaturated carboxylic acid anhydride is 0.5 to 5 percent based on the total mass of the acid-modified propylene-containing polymer.
7. The chlorinated polypropylene resin according to any one of claims 1 to 6, wherein the chlorinated polypropylene resin contains a metal ion shielding agent and/or an antioxidant having a function of complexing metal ions;
preferably, the metal ion shielding agent comprises one or more of 1,2 bis- [ beta- (3, 5-di-tert-butyl-4-hydroxy) propylacyl ] hydrazine, triethanolamine, pentamethyldiethylenetriamine and 2, 2-bipyridine;
preferably, the antioxidant having a complexing metal ion effect comprises one or more of the antioxidants IrganoxMD 1024, NouguardXL-1, RIANOX MD-1024, RIANOX MD-697 and RIANOX 1019;
preferably, the addition amount of the metal ion shielding agent and the antioxidant with the function of complexing metal ions is 0.1 to 0.5 percent of the weight of the chlorinated polypropylene resin.
8. A method for preparing the chlorinated polypropylene resin of any one of claims 1-7.
9. The method as claimed in claim 8, wherein the chlorinated polypropylene is synthesized by dissolving polypropylene as a raw material in a chlorine-containing solvent, introducing chlorine gas, and performing a radical substitution reaction.
10. Use of a chlorinated polypropylene resin, which is the chlorinated polypropylene resin according to any one of claims 1 to 7 or the chlorinated polypropylene resin produced by the production method according to claim 8 or 9, for an ink composition for gravure printing or offset printing.
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